KR20210132679A - Coating liquid for forming an anti-glare film, an anti-glare film, and a laminate having the same - Google Patents

Abstract

A coating liquid for forming an anti-glare film comprising the following components. Component (A): The 1st metal alkoxide represented by following formula (I), its hydrolyzate, or its partial condensate. R ¹ _m M ¹ (OR ² ) _nm (I) Component (B): A metal salt containing at least one selected from a metal salt represented by the following formula (II) and an ^{oxalate of M 2 in the following formula (II).} M ² (X) _k (II) Solvent group (A): at least one selected from glycol ethers having a boiling point of less than 160°C, derivatives thereof, and ketones. Solvent group (B): At least 1 sort(s) selected from alcohol with a boiling point of 120 degrees C or less. Definitions of symbols in Formulas 1 and 2 are as described in the specification.

Description

Coating liquid for forming an anti-glare film, an anti-glare film, and a laminate having the same

The present invention provides a coating liquid for forming an anti-glare film that is excellent in anti-glare properties (anti-glare function) and can form an anti-glare film having a high refractive index on a glass substrate, and an anti-glare film obtained from the coating liquid It relates to an overt coating and a laminate provided with the same.

The image display apparatus (liquid crystal display, organic EL display, plasma display, etc.) equipped with various devices, such as a television, a personal computer, and a smart phone, is reflected when external light, such as indoor lighting (fluorescent lamp, etc.) and sunlight, is reflected on a display surface. The visibility of an image may fall by an image.

As a method of suppressing the penetration of external light, there is a method in which an anti-glare treatment (anti-glare treatment) is performed on a display surface of an image display device. The anti-glare treatment is a treatment for forming irregularities on the surface, and the effect of diffusely reflecting external light (anti-glare effect) is obtained by the formed irregularities.

As a method of the anti-glare treatment, a treatment for etching the surface of a transparent substrate such as glass with a chemical such as hydrofluoric acid (see Patent Document 1), a treatment for forming an organic anti-glare film having irregularities on the surface (see Patent Document 2), etc. has been proposed.

Japanese Patent No. 5839134 International Publication 2018/070426

However, in the treatment of etching the surface of the glass substrate with a chemical, the risk of the chemical becomes a problem, and in the treatment of forming an organic anti-glare film on the surface, the coating property to the glass substrate or the formation of an additional functional film on the film A problem arises in the coating property and adhesiveness at the time of it.

From the above points, the present invention provides a coating liquid for forming an anti-glare film, which is excellent in anti-glare properties (anti-glare function), can be formed on a glass substrate and can form an anti-glare film having a high refractive index, and its application It aims at provision of the anti-glare film obtained from a liquid, and the laminated body provided with the same.

MEANS TO SOLVE THE PROBLEM This inventor came to complete this invention which has the following summary, as a result of advancing earnest research in order to achieve the said objective. That is, this invention has the following structural requirements.

1. A coating liquid for forming an anti-glare film containing the following components.

Component (A): The 1st metal alkoxide represented by following formula (I), its hydrolyzate, or its partial condensate.

R ¹ _m M ¹ (OR ² ) _nm (I)

(wherein, M ¹ is silicon (Si), titanium (Ti), tantalum (Ta), zirconium (Zr), boron (B), aluminum (Al), magnesium (Mg), tin (Sn) and zinc ( Zn) represents at least one metal selected from the group consisting of. R ¹ may be substituted with a hydrogen atom or a fluorine atom, and a halogen atom, a vinyl group, a glycidoxy group, a mercapto group, a methacryloxy group, acryl represents a hydrocarbon group having 1 to 20 carbon atoms which may be substituted with an oxy group, an isocyanate group, an amino group or a ureide group, and which may have a hetero atom, R ² represents an alkyl group having 1 to 5 carbon atoms, n is M ^It represents valence 2 to 5 of ^1. m is 0 or 1 when the valence of M 1 is 2, 0 to 2 when the valence of ^{M 1} is 3, and 0 to 3 when the valence of ^{M 1 is 4.} Any of 0 to 4 when the mantissa of ^{M 1 is 5.)}

Component (B): A metal salt containing at least one selected from the metal salt represented by the following formula (II) and ^{the oxalate of M 2 in the following formula (II).}

M ² (X) _k (II)

(wherein, M ² is aluminum (Al), indium (In), zinc (Zn), zirconium (Zr), bismuth (Bi), lanthanum (La), tantalum (Ta), yttrium (Y) and cerium ( Ce) represents at least one metal selected from the group consisting of, X represents chlorine, nitric acid, sulfuric acid, acetic acid, sulfamic acid, sulfonic acid, acetoacetic acid, acetylacetonate or a basic salt thereof, and k represents M ² represents the singer of

Solvent group (A): At least 1 sort(s) selected from glycol ether with a boiling point of less than 160 degreeC, its derivative(s), or ketones.

Solvent group (B): At least 1 sort(s) selected from the alcohols with a boiling point of 120 degrees C or less.

By using the coating liquid for anti-glare film formation of this invention, while being excellent in anti-glare property (anti-glare function), it can form on a glass substrate, and can form the anti-glare film which has a high refractive index.

BRIEF DESCRIPTION OF THE DRAWINGS It is the image which observed the board|substrate with an anti-glare film obtained in Example 2 with the three-dimensional white interference microscope Contour GT.
It is the image which observed the board|substrate with an anti-glare film obtained in the comparative example 2 with the three-dimensional white interference microscope Contour GT.

Each component contained in the coating liquid for forming an anti-glare film of the present invention will be described in detail below.

<Component (A)>

The component (A) which the coating liquid for anti-glare film formation of this invention contains is the 1st metal alkoxide represented by following formula (I), its hydrolyzate, or its partial condensate.

R ¹ _m M ¹ (OR ² ) _nm (I)

where M ¹ is silicon (Si), titanium (Ti), tantalum (Ta), zirconium (Zr), boron (B), aluminum (Al), magnesium (Mg), tin (Sn) and zinc (Zn) ) represents at least one or more metals selected from the group consisting of. Among them, silicon, titanium, zirconium, aluminum, and tin are preferable from the viewpoints of availability and storage stability of the composition.

R ¹ may be substituted with a hydrogen atom or a fluorine atom, and may be substituted with a halogen atom, a vinyl group, a glycidoxy group, a mercapto group, a methacryloxy group, an acryloxy group, an isocyanate group, an amino group or a ureide group. , and a hydrocarbon group having 1 to 20 carbon atoms which may have a hetero atom. Especially, from a viewpoint of availability and stability, as a substituent, a vinyl group, a mercapto group, a methacryloxy group, an acryloxy group, and a ureide group are preferable, and a C1-C10 hydrocarbon group is preferable.

R<^2> represents a C1-C5 alkyl group, and especially, C1-C4 is preferable from a viewpoint of availability and storage stability of a composition.

n represents valences 2 to 5 of ^{M 1 .} m is 0 or 1 when the valence of ^{M 1 is 2, 0 or 2 when the valence of M 1} is 3, any of 0-3 when ^{the valence of M 1} is 4, and the valence of ^{M 1 is} If it is 5, it is any of 0 to 4.

As for the component (A) which the coating liquid for anti-glare film formation of this invention contains, especially, the partial condensate of a silicon alkoxide, a titanium alkoxide, or a zirconium alkoxide is preferable. Specific examples include ^{partial condensates of metal alkoxides represented by the formula (I) in which M 1} is selected from any of silicon (Si), titanium (Ti), tantalum (Ta), and zirconium (Zr). have.

<Component (B)>

The component (B) contained in the coating liquid for forming an anti-glare film of the present invention contains at least one metal salt selected from ^{a metal salt represented by the following formula (II) and an oxalate of M 2 in the following formula (II).} .

M ² (X) _k (II)

In the formula, M ² is aluminum (Al), indium (In), zinc (Zn), zirconium (Zr), bismuth (Bi), lanthanum (La), tantalum (Ta), yttrium (Y) and cerium (Ce) ) represents at least one metal selected from the group consisting of X represents chlorine, nitric acid, sulfuric acid, acetic acid, sulfamic acid, sulfonic acid, acetoacetic acid, acetylacetonate, or a basic salt thereof. Among them, nitrates of aluminum, indium, and cerium are preferable from the viewpoints of availability and storage stability of the composition.

k represents a valence of M ^2.

<Other ingredients>

In the coating liquid for forming an anti-glare film of the present invention, components other than the above components, for example, inorganic fine particles, metaloxane oligomers, metaloxane polymers, leveling agents, surfactants, etc. may be contained. .

As the inorganic fine particles, fine particles such as silica fine particles, alumina fine particles, titania fine particles and magnesium fluoride fine particles are preferable, and a colloidal solution of these inorganic fine particles is particularly preferable. What disperse|distributed the inorganic fine particle in the dispersion medium may be sufficient as this colloidal solution, and the colloidal solution of a commercial item may be sufficient as it.

In this invention, it becomes possible by containing an inorganic fine particle to provide the surface shape and other functions of the anti-glare film formed. As an inorganic fine particle, it is preferable that the average particle diameter is 0.001-0.2 micrometer, More preferably, it is 0.001-0.1 micrometer.

Water and an organic solvent are mentioned as a dispersion medium of an inorganic fine particle. As a colloidal solution, from a viewpoint that stability of the coating liquid for anti-glare film formation improves, it is preferable that pH or pKa is adjusted to 1-10, More preferably, it is 2-7.

Examples of the organic solvent used for the dispersion medium of the colloidal solution include methanol, ethanol, propanol, butanol, ethylene glycol, propylene glycol, butanediol, pentanediol, 2-methyl-2,4-pentanediol, diethylene glycol, dipropylene glycol, ethylene. alcohols such as glycol monopropyl ether; ketones such as methyl ethyl ketone and methyl isobutyl ketone; aromatic hydrocarbons such as toluene and xylene; amides such as dimethylformamide, dimethylacetamide, and N-methyl-2-pyrrolidone; esters such as ethyl acetate, butyl acetate, and γ-butyrolactone; Ethers, such as tetrahydrofuran and 1, 4- dioxane, are mentioned. Among these, alcohols and ketones are preferable. These organic solvents can be used individually or in mixture of 2 or more types as a dispersion medium.

<Solvent group (A)>

The solvent group (A) contained in the coating liquid for forming an anti-glare film of the present invention is at least one selected from glycol ethers having a boiling point of less than 160°C, derivatives thereof, and ketones. Specifically, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol di Glycol ethers and derivatives thereof, such as propyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monomethyl ether acetate, propylene glycol dimethyl ether, propylene glycol diethyl ether, acetone, methyl ethyl ketone, methyl isobutyl Although ketones, such as a ketone, are mentioned, Especially from a viewpoint of application stability, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol diethyl ether, ethylene glycol dipropyl ether, propylene glycol monomethyl ether, propylene glycol Monoethyl ether, propylene glycol monomethyl ether acetate, and methyl isobutyl ketone are preferable.

<Solvent group (B)>

The solvent group (B) contained in the coating liquid for forming an anti-glare film of the present invention is at least one selected from alcohols having a boiling point of 120°C or lower. Specific examples thereof include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methyl-1-propanol, and 2-methyl-2-propanol. Among them, storage of the composition From the viewpoint of stability, methanol, ethanol, 2-propanol, 2-butanol, and 2-methyl-1-propanol are preferable.

<Other solvents>

The coating liquid for forming an anti-glare film of the present invention may optionally contain solvents other than the solvent groups (A) and (B) (hereinafter, also referred to as other solvents) from the viewpoint of stability of the coating liquid or the like.

Examples of the other solvent include alcohols such as hexanol, heptanol, octanol, nonanol, decanol, undecanol, dodecanol and diacetone alcohol, ethylene glycol, diethylene glycol, dipropylene glycol, 2-methyl- Glycols such as 2,4-pentanediol, propanediol, butanediol, pentanediol, hexanediol, heptanediol, ethylene glycol monobutyl ether, ethylene glycol dibutyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether, propylene glycol dipropyl ether, propylene glycol dibutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, Glycol ethers, such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, and diethylene glycol dibutyl ether, Esters, such as methyl acetate, ethyl acetate, ethyl lactate, N-methyl-2 -pyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, γ-butyrolactone, dimethylsulfoxide, tetramethylurea, hexamethylphosphotriamide, m-cresol, tetrahydrofuran, etc. can be heard Among them, from the viewpoint of availability and storage stability of the composition, ethylene glycol, diethylene glycol, 2-methyl-2,4-pentanediol, propanediol, butanediol, ethylene glycol monobutyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, diethylene glycol dimethyl ether, Diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, N-methyl-2-pyrrolidone, N,N-dimethylformamide and tetrahydrofuran are preferably used.

<Coating solution for forming an anti-glare film and an anti-glare film>

The coating liquid for forming an anti-glare film of the present invention is at least selected from ^{a metal salt represented by the formula (II) and an oxalate of M 2} in the formula (II) for the first metal alkoxide represented by the formula (I). It is obtained by hydrolyzing and condensing in an organic solvent in presence of 1 type of metal salt, and adding a solvent suitably after that. The solvents of solvent groups (A) and (B) are added in the solvent addition process at the time of the said hydrolysis/condensation and or thereafter. In addition, at this time, other solvents may also be added suitably as needed.

The content ratio of the metal atom (M ¹ ) of the metal alkoxide and the metal atom (M ² ) of the metal salt preferably satisfies the relationship of ^{0.01 ≤ M 2} /(M ¹ + M ^{2 ) ≤ 0.7 in terms of molar ratio.} . When this value is less than 0.01, it is not preferable because the mechanical strength of the film obtained is not enough. On the other hand, when 0.7 is exceeded, the adhesiveness of the metal oxide layer with respect to base materials, such as a glass substrate, will fall. Moreover, when baking at the low temperature of 450 degreeC or less, there exists a tendency for the chemical-resistance of the metal oxide layer obtained to fall. In addition, when there are multiple types of metal atoms of the metal alkoxide contained in the coating composition, the metal atom (M ¹ ) means the sum of multiple types of metal atoms, and when the metal atoms of the metal salt contained in the coating composition are multiple types , The metal atom (M ² ) means the sum of a plurality of types of metal atoms.

As for the solid content concentration in the coating liquid for forming an anti-glare film, when the metal alkoxide and the metal salt are converted into metal oxides, the solid content is preferably in the range of 0.5 to 20 mass%. When the solid content exceeds 20% by mass, the storage stability of the coating composition deteriorates, and the film thickness control of the anti-glare film becomes difficult. On the other hand, when solid content is 0.5 mass % or less, the thickness of the anti-glare film obtained becomes thin, and in order to obtain a predetermined|prescribed film thickness, multiple application|coating is needed.

The coating liquid for anti-glare film formation represents the 1st metal alkoxide (for example, a silicon alkoxide or a titanium alkoxide) represented by the said Formula (I) by the said Formula (II), The metal salt and the said Formula (II) It is obtained by hydrolyzing and condensing in an organic solvent in the presence of at least 1 sort(s) of metal salt (for example, aluminum salt) selected from the oxalate of M<^{2> in in.} The amount of water used for hydrolysis of silicon alkoxide, titanium alkoxide, or silicon alkoxide and titanium alkoxide is a molar ratio with respect to the total number of moles of silicon alkoxide, titanium alkoxide, or silicon alkoxide and titanium alkoxide. It is preferable to set it as 0.5-24 in conversion. More preferably, it is 0.5-20. When the molar ratio (amount of water (mol)/(total number of moles of metal alkoxide)) is 0.5 or less, hydrolysis of the metal alkoxide becomes insufficient, and the film formability is reduced, the strength of the obtained anti-glare film is reduced, Therefore, it is not advisable Moreover, when the molar ratio is more than 24, since polycondensation continues to advance, since storage stability is reduced, it is unpreferable. It is the same also when using another metal alkoxide.

Moreover, even when other metal alkoxides are used, it is preferable to select the same conditions with respect to the addition amount of water.

In the hydrolysis process when preparing the coating liquid for forming an anti-glare film, when the coexisting metal salt (eg, aluminum salt) is a water-containing salt, the water content is involved in the reaction, so it is used for hydrolysis. It is necessary to consider the water content of the metal salt (eg, aluminum salt) with respect to the amount of water.

The coating liquid for forming an anti-glare film is produced by hydrolyzing and condensing a metal alkoxide, and by selecting the composition of the metal alkoxide, it is possible to adjust the refractive index of the anti-glare film obtained within a predetermined range. For example, when a silicon alkoxide and a titanium alkoxide are selected as a metal alkoxide, the anti-glare film obtained within the predetermined range mentioned later, specifically within the range of 1.45-2.1 by adjusting the mixing ratio. It is possible to adjust the refractive index of From the viewpoint of preventing reflection of the laminate provided with the anti-glare film of the present invention, the refractive index of the anti-glare film of the present invention is preferably 1.48 to 1.8.

In other words, if the refractive index required for the anti-glare film after application of the anti-glare film-forming coating liquid and firing is determined, it is possible to determine the composition molar ratio of the silicon alkoxide and the titanium alkoxide according to the refractive index. Although this composition molar ratio is arbitrary, the refractive index of the anti-glare film from the coating liquid for anti-glare film formation obtained by hydrolyzing only silicon alkoxide, for example is a value of about 1.45. And the refractive index of the metal oxide layer from the coating composition obtained by hydrolyzing only a titanium alkoxide is a value of about 2.1. Therefore, when it is desired to set the refractive index of the anti-glare film between 1.45 to 2.1, it is possible to prepare a coating composition using silicon alkoxide and titanium alkoxide in a predetermined ratio according to a refractive index value within that range.

Moreover, adjustment of the refractive index of the anti-glare film obtained also by using another metal alkoxide is possible.

In addition, about the refractive index of an anti-glare film, it can also adjust by selecting film-forming conditions other than composition conditions. By doing in this way, it is possible to realize the desired refractive index value of the anti-glare film.

That is, when baking the coating film of the coating liquid for anti-glare film formation and manufacturing an anti-glare film, the refractive index of an anti-glare film fluctuates according to the baking temperature. In this case, the higher the firing temperature, the higher the refractive index of the anti-glare coating. Therefore, it is possible to adjust the refractive index of the anti-glare film obtained by selecting the calcination temperature to an appropriate value. And when heat resistance of a base material etc. is considered, the range of 100 degreeC - 300 degreeC is preferable, and, as for the calcination temperature, it is more preferable to set it as the range of 150 degreeC - 250 degreeC.

Moreover, when the coating liquid for anti-glare film formation contains a titanium alkoxide, when an ultraviolet-ray (UV) is irradiated to a coating film before baking, the refractive index of the anti-glare film obtained will fluctuate. Specifically, the refractive index of the anti-glare coating can be increased as the amount of ultraviolet irradiation is increased. Therefore, it is possible to select the presence or absence of ultraviolet irradiation to realize a desired refractive index. In the anti-glare film, when a desired refractive index can be realized by selection of conditions such as composition, ultraviolet irradiation is not required. And when performing ultraviolet irradiation, it is possible to adjust the refractive index of an anti-glare film by selecting the irradiation amount. Anti-glare coating WHEREIN: When ultraviolet irradiation is required in order to obtain a desired refractive index, a high pressure mercury lamp can be used, for example. And when a high-pressure mercury lamp is used, the irradiation amount of 1000 mJ/cm<2> or more of total light irradiation in conversion of 365 nm is preferable, and the irradiation amount of 3000 mJ/cm<2> - 10000 mJ/cm<2> is more preferable. In addition, there is no designation in particular as a UV light source, Another UV light source can also be used. In the case of using another light source, the same amount of integrated light as in the case of using the high-pressure mercury lamp is sufficient.

However, especially when a coating liquid for anti-glare film formation contains a titanium alkoxide component, it has the property that a viscosity rises gradually under room temperature storage. Although there is no fear of becoming a big problem in practical use, when the thickness of the anti-glare film is precisely controlled, careful management of temperature and the like is required. Moreover, such a raise of a viscosity becomes remarkable as the composition ratio of the titanium alkoxide in a coating composition increases. This is considered because a titanium alkoxide has a large hydrolysis rate with respect to a silicon alkoxide etc., and a condensation reaction is quick.

When the coating liquid for forming an anti-glare film contains a titanium alkoxide component, in order to reduce the change in viscosity, for example, after mixing in a solvent such as a metal salt and alcohol, the silicon alkoxide and the titanium alkoxide are hydrolyzed. ways to do it can be found. In this method, thereafter, by mixing glycol or a derivative thereof, the stability of the condensate is improved, and a coating liquid for forming an anti-glare film with little change in viscosity is obtained.

The above-described coating liquid for forming an anti-glare film can be made into fine droplets at the time of application and deposited on a substrate to obtain a metal oxide film having anti-glare properties. As an application|coating method, spray application|coating, mist application|coating, inkjet application|coating, etc. are mentioned, Especially, spray application|coating and inkjet application|coating are preferable.

<Laminate>

The laminate of this invention is obtained by apply|coating and baking the coating liquid for anti-glare film formation on various board|substrates including a glass substrate, and forming an anti-glare film. It is possible to form various functional films, such as an antireflection film, into a film on this anti-glare film corresponding to the function requested|required of a laminated body.

Here, the antireflection film has the effect of reducing the reflectance, and in addition to reducing glare due to the reflection of light, when used in an image display device, the transmittance of light from the image display device can be improved, and the visibility of the image display device can be improved. It is a membrane that can be improved.

The structure of the antireflection film is not particularly limited as long as it is a structure capable of suppressing light reflection, and examples thereof include a film having a lower refractive index than the anti-glare film (hereinafter also referred to as a low refractive index film).

As a material constituting the low-refractive-index film, polysiloxane having a silicon atom to which a fluorinated organic group is bonded is exemplified.

As a method of forming an antireflection film, a spin coating method, a dip coating method, a casting method, a slit coating method, a spray coating method, and an electrostatic spray deposition method on the surface of an adhesion layer formed on the anti-glare film or other functional film (ESD method) or the like, followed by heat treatment if necessary, or physical vapor deposition (PLD method) such as chemical vapor deposition (CVD), sputtering, or PLD on the surface of the adhesion layer.

In addition, the laminate of the present invention may further laminate an antifouling film on the anti-glare film or on the anti-reflection film. An antifouling film is a film that suppresses adhesion of organic or inorganic substances to a surface, or a film that has the effect of easily removing the adherent by cleaning such as wiping even when organic or inorganic substances are adhered to the surface. am.

The thickness of the antifouling film is not particularly limited, but when the antifouling film is made of a fluorinated organosilicon compound film, the film thickness is preferably 2 to 20 nm, more preferably 2 to 15 nm, more preferably 2 to 10 nm more preferably. If the film thickness is 2 nm or more, it will be in a state uniformly covered with an antifouling|stain-resistant layer, and will endure practical use from a viewpoint of abrasion resistance. Moreover, optical characteristics, such as a haze value of the anti-glare-film board|substrate in the state in which the antifouling|stain-resistant film was formed as a film thickness is 20 nm or less, are favorable.

The anti-glare coating substrate has an in-plane standard deviation of the haze of 1 to 40%, more preferably 1 to 30%. If it is this range, when the board|substrate with an anti-glare film is visually recognized from the user side, it can visually recognize as if a homogeneous anti-glare film process had been performed, and it is excellent in aesthetics. Moreover, the touch sensitivity by the unevenness|corrugation of an anti-glare film is not impaired.

<Use>

The use of the anti-glare coating substrate of the present invention is not particularly limited. Specific examples include transparent parts for vehicles (headlight covers, side mirrors, front transparent substrates, side transparent substrates, rear transparent substrates, instrument panel surfaces, etc.), meters, architectural windows, show windows, displays (laptop computers, monitors, LCDs, PDP, ELD, CRT, PDA, etc.), LCD color filters, touch panel substrates, pickup lenses, optical lenses, spectacle lenses, camera parts, video parts, CCD cover substrates, optical fiber end face, projector parts, copier parts , transparent substrates for solar cells (cover glass, etc.), mobile phone windows, backlight unit parts (light guide plate, cold cathode tube, etc.), backlight unit parts liquid crystal brightness enhancement film (prism, transflective film, etc.), liquid crystal brightness enhancement film, Organic EL light emitting element parts, inorganic EL light emitting element parts, phosphor light emitting element parts, optical filters, cross-sections of optical parts, lighting lamps, lighting equipment covers, amplified laser light sources, anti-reflection films, polarizing films, agricultural films, etc. have.

Example

Hereinafter, the present invention will be described in more detail by way of Examples, but the present invention is not limited thereto.

Abbreviations used below are as follows.

TEOS: tetraethoxysilane

F13: tridecafluorooctyltrimethoxysilane

UPS: γ-ureidopropyltriethoxysilane

MPMS: 3-methacryloxypropyltrimethoxysilane

TTE: Tetraethoxytitanium

TIPT: Tetraisopropoxytitanium

AN: aluminum nitrate hexahydrate

MeOH: methanol

EtOH: ethanol

IPA: Isopropanol

BCS : Butyl Cellosolve

PGME: propylene glycol monomethyl ether

PGMEA: Propylene glycol monomethyl ether acetate

PG: propylene glycol

HG: 2-methyl-2,4-pentanediol

<Synthesis Example 1>

In a flask with a capacity of 200 mL, AN (2.9 g), water (2.7 g), and EtOH (50.3 g) were added and stirred to obtain an AN solution. TEOS (23.1 g) was added to this AN solution, and it stirred at room temperature for 30 minutes. Then, TTE (8.4 g) and EtOH (12.6 g) were added, and also it stirred at room temperature for 30 minutes, and obtained solution K1.

<Synthesis Example 2>

In a 200 mL flask, AN (2.9 g), water (2.6 g), and EtOH (50.6 g) were added and stirred to obtain an AN solution. TEOS (21.2 g) was added to this AN solution, and it stirred at room temperature for 30 minutes. Then, TTE (10.0 g) and EtOH (12.7 g) were added, and it stirred at room temperature for 30 minutes, and obtained solution K2.

<Synthesis Example 3>

In a 200 mL flask, AN (2.8 g), water (2.6 g), and EtOH (51.2 g) were added and stirred to obtain an AN solution. TEOS (17.7 g) was added to this AN solution, and it stirred at room temperature for 30 minutes. Then, TTE (12.9 g) and EtOH (12.8 g) were added, and it stirred at room temperature for 30 minutes, and obtained solution K3.

<Synthesis Example 4>

In a flask with a capacity of 200 mL, AN (2.9 g), water (2.7 g), EtOH (24.3 g), and IPA (24.3 g) were added and stirred to obtain an AN solution. 23.1 g of TEOS was added to this AN solution, and it stirred at room temperature for 30 minutes. Then, TIPT (10.5 g), EtOH (6.1 g), and IPA (6.1 g) were added, and it stirred at room temperature for 30 minutes, and obtained solution K4.

<Synthesis Example 5>

To a 200 mL four-necked flask equipped with a reflux tube, TEOS (34.7 g) and MeOH (33.0 g) were added and stirred, and thereto, MeOH (16.4 g), water (15.0 g), 60% aqueous nitric acid solution (0.9 g) was added, and it stirred for 30 minutes in a 10 degreeC ice bath. Then, it refluxed for 3 hours, it stood to cool to room temperature, and the solution K5 was obtained.

<Synthesis Example 6>

To a 200 mL four-necked flask equipped with a reflux tube, TEOS (29.0 g), F13 (10.5 g), and MeOH (27.9 g) were added and stirred, thereto, MeOH (14.0 g), water (15.0 g), Oxalic acid (0.8 g) was added, and it stirred in a 10 degreeC ice bath for 30 minutes. Then, it stirred at 65 degreeC for 2 hours, UPS (1.4g) and MeOH (1.4g) were added after that, and also it was made to react at 65 degreeC for 2 hours. Then, it stood to cool to room temperature, and the solution K6 was obtained.

<Synthesis Example 7>

In a 200 mL flask, AN (2.8 g), water (2.5 g), and EtOH (51.0 g) were added and stirred to obtain an AN solution. To the AN solution, TEOS (15.9 g) and MPMS (2.1 g) were added, followed by stirring at room temperature for 30 minutes. Then, TTE (12.9 g) and EtOH (12.8 g) were added, and also it stirred at room temperature for 30 minutes, and obtained solution K7.

<Synthesis Example 8>

In a 200 mL flask, AN (2.8 g), water (2.5 g), and EtOH (38.3 g) were added and stirred to obtain an AN solution. TEOS (16.8 g) was added to this AN solution, and it stirred at room temperature for 30 minutes. Thereafter, TTE (12.9 g) and EtOH (12.8 g) were added, followed by stirring at room temperature for 30 minutes. Then, UPS (1.1 g) and EtOH (12.8 g) were added, and it stirred at room temperature for 30 minutes. A solution K8 was obtained.

<Preparation Example 1>

To 60 g of K1 solution, PGME (10 g) and EtOH (30 g) were added to obtain a solution KL1.

<Preparation Examples 2 to 7>

PGME (30 g) and EtOH (10 g) were added to K2 to K5 and K7 to K8 solutions (60 g) to obtain solutions KL2 to KL5 and KL7 to KL8, respectively.

<Preparation Example 8>

To the K1 solution (60 g), EtOH (40 g) was added to obtain a solution KM1.

<Preparation Example 9>

To the K1 solution (60 g), HG (10 g), BCS (10 g), and IPA (20 g) were added to obtain a solution KM2.

<Preparation Example 10>

To the K5 solution (60 g), PGMEA (30 g) and MeOH (10 g) were added to obtain a solution KM3.

<Preparation Example 11>

To a K6 solution (20 g), PG (5 g) and MeOH (75 g) were added to obtain a solution KL6.

[Spray application]

Spray application was performed on the apparatus and conditions shown below.

Device name: Apyros Co., Ltd. spray coater API-240-3D

<Application condition I>

Nozzle height: 100 mm, Y-axis pitch: 5 mm, Air pressure: 560 kPa, chemical liquid flow rate: 2 cc/min, nozzle speed: 170 mm/sec

<Application condition II>

Nozzle height: 100 mm, Y-axis pitch: 5 mm, Air pressure: 560 kPa, chemical flow rate 2 cc/min, nozzle speed: 250 mm/sec

<Application condition III>

Nozzle height: 100 mm, Y-axis pitch: 7 mm, Air pressure: 560 kPa, chemical flow rate: 4.9 cc/min, nozzle speed: 400 mm/sec

[Firing conditions]

It dried at the temperature of 70 degreeC on the hotplate for 3 minutes, and baked at 200 degreeC for 30 minutes with hot-air circulation type oven.

[Discharge Stability]

When it was possible to discharge without clogging, it was set as (circle), when clogging occurred in the middle of application|coating and it was set as x.

[HAZE, total light transmittance]

Soda-lime glass was used for the board|substrate, and it formed into a film under application|coating conditions I or II by spray application. HAZE and total light transmittance were measured for the obtained board|substrate with a film by Suga Testing Instruments Co., Ltd. product haze meter HZ-V3.

[Surface observation]

Soda-lime glass was used for the board|substrate, and it formed into a film under application|coating conditions I or II by spray application. The obtained board|substrate with a film was observed with the Bruker Japan Co., Ltd. product three-dimensional white interference microscope Contour GT.

[Refractive Index]

A silicon substrate 100 is used for the substrate, and solutions KL2 to KL5, KL7 to KL8 and KM2 are formed by spin coating so that the film thickness after firing becomes 100 nm, and dried on a hot plate at a temperature of 70° C. for 3 minutes, followed by hot air. It baked at 200 degreeC by circulation type oven for 30 minutes. Using the obtained board|substrate with a film, the refractive index in wavelength 633nm was measured with the ellipsometer (The Mizojiri Optical Industrial Co., Ltd. make, DVA-FLVW).

As shown in Table 1, in Examples 1-7, and 11-12, discharge stability is maintained. Moreover, the HAZE value is rising, and the uneven|corrugated shape was observed on the surface also from an interference microscope image. It is suggested that the anti-glare film was formed from the above point.

In Comparative Example 1, since the solvent (A) component was not contained, discharge stability was insufficient, clogging occurred in the nozzle, and film formation was difficult. Moreover, about the comparative example 2, since 150 degreeC or more solvent was included, HAZE did not rise, and it was observed that the surface is flat also in an interference microscope image, and anti-glare property did not express.

[LR unveiling]

KL2-KL4 and KM3 were formed into a film on the glass substrate under application|coating conditions II by spray application|coating, and the board|substrate with an anti-glare film was produced.

Moreover, when the refractive index was measured using KM3, the refractive index was 1.43. In addition, the HAZE of the board|substrate formed into a film using KM3 was 10.

On the said board|substrate with an anti-glare film, KL6 was formed into a film by spray application|coating as an antireflection layer under application|coating conditions III.

[reflectivity]

A spectral reflectance curve obtained by measuring the reflectance in a wavelength range of 380 nm to 800 nm at an incident angle of 5° of light with an ultraviolet visible near-infrared spectrophotometer UV-3600 manufactured by Shimadzu Corporation using the prepared substrate. From , according to JISR 3106, the average luminous reflectance was obtained.

About Examples 8-10, surface reflection was suppressed by providing an antireflection layer. About Comparative Example 3, although anti-glare property could be expressed, since the refractive index was low, even if it formed an antireflection layer, the effect of reflection suppression was hardly expressed.

Industrial Applicability

By using the coating liquid for forming an anti-glare film of the present invention, it is possible to form an anti-glare film that is excellent in anti-glare properties (anti-glare function) and can be formed on a glass substrate and has a high refractive index, and a laminate comprising the same. it becomes possible Thereby, it can contribute to the improvement of the display quality of the image display apparatus (liquid crystal display, organic electroluminescent display, plasma display, etc.) equipped with various devices, such as a television, a personal computer, and a smart phone.

Claims (13)

A coating liquid for forming an anti-glare film comprising the following components.
Component (A): The 1st metal alkoxide represented by following formula (I), its hydrolyzate, or its partial condensate.
R ¹ _m M ¹ (OR ² ) _nm (I)
(wherein, M ¹ is silicon (Si), titanium (Ti), tantalum (Ta), zirconium (Zr), boron (B), aluminum (Al), magnesium (Mg), tin (Sn) and zinc ( Zn) represents at least one metal selected from the group consisting of. R ¹ may be substituted with a hydrogen atom or a fluorine atom, and a halogen atom, a vinyl group, a glycidoxy group, a mercapto group, a methacryloxy group, acryl represents a hydrocarbon group having 1 to 20 carbon atoms which may be substituted with an oxy group, an isocyanate group, an amino group or a ureide group, and which may have a hetero atom, R ² represents an alkyl group having 1 to 5 carbon atoms, n is M ^It represents valence 2 to 5 of ^1. m is 0 or 1 when the valence of M 1 is 2, 0 to 2 when the valence of ^{M 1} is 3, and 0 to 3 when the valence of ^{M 1 is 4.} Any of 0 to 4 when the mantissa of ^{M 1 is 5.)}
Component (B): A metal salt containing at least one selected from the metal salt represented by the following formula (II) and ^{the oxalate of M 2 in the following formula (II).}
M ² (X) _k (II)
(wherein, M ² is aluminum (Al), indium (In), zinc (Zn), zirconium (Zr), bismuth (Bi), lanthanum (La), tantalum (Ta), yttrium (Y) and cerium ( Ce) represents at least one metal selected from the group consisting of, X represents chlorine, nitric acid, sulfuric acid, acetic acid, sulfamic acid, sulfonic acid, acetoacetic acid, acetylacetonate or a basic salt thereof, and k represents M ² represents the singer of
Solvent group (A): At least 1 sort(s) chosen from glycol ether with a boiling point of less than 160 degreeC, its derivative(s), or ketones.
Solvent group (B): At least 1 sort(s) selected from alcohol with a boiling point of 120 degrees C or less. The method of claim 1,
Solvent group (A) A, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, Glycol ethers and derivatives thereof such as ethylene glycol dipropyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monomethyl ether acetate, propylene glycol dimethyl ether, propylene glycol diethyl ether, acetone, methyl ethyl ketone, A coating liquid for forming an anti-glare film, which is at least one selected from ketones such as methyl isobutyl ketone. The method of claim 1,
The solvent group (B) is at least one selected from methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methyl-1-propanol, and 2-methyl-2-propanol; A coating solution for forming an overt film. The method of claim 1,
A coating liquid for forming an anti-glare film, wherein the content of the solvent group (A) is 5 to 70 mass% of the total solvent. The method of claim 1,
The formula (1) of the M ¹ is silicon, titanium, zirconium, aluminum, tin, room overt coating liquid for forming a coating film. The method of claim 1,
The coating liquid for anti-glare film formation whose component (A) of Claim 1 is a partial condensate of a silicon alkoxide, a titanium alkoxide, and a zirconium alkoxide. The method of claim 1,
The formula [2] of M ² is aluminum, indium, cerium the room overt coating liquid for forming a coating film. A method for producing an anti-glare film, wherein the coating liquid for forming an anti-glare film according to any one of claims 1 to 6 is applied to a substrate by spray application. An anti-glare film obtained from the coating liquid for forming an anti-glare film according to any one of claims 1 to 7. 10. The method of claim 9,
An anti-glare film with a refractive index of 1.48 to 1.8. A laminate provided with the anti-glare film of Claim 9 or 10. 12. The method of claim 11,
The laminate has an in-plane standard deviation of haze of 1 to 40%. A laminate in which an antireflection film is laminated on the anti-glare film according to claim 9 or 10.

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